Synthesis and Multi-Mode Luminescence Properties of Cs2ZnCl4∶Ce3+，Mn2+

doi:10.19894/j.issn.1000-0518.230189

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (12): 1613-1622.DOI: 10.19894/j.issn.1000-0518.230189

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Synthesis and Multi-Mode Luminescence Properties of Cs₂ZnCl₄∶Ce³⁺，Mn²⁺

Tian-Cheng ZHENG, Yue LI, Yu-Ling LIU, Yong-Bo MA, Xi-Yan LI()

The Institute of Photoelectronic Thin Film Devices and Technology，College of Electronic Information and Optical Engineering，Nankai University，Tianjin 300381，China

Received:2023-07-05 Accepted:2023-11-18 Published:2023-12-01 Online:2024-01-03
Contact: Xi-Yan LI
About author:xiyan.li@nankai.edu.cn
Supported by:
the National Natural Science Foundation of China(22005152)

Abstract

Abstract:

In recent years， low-dimensional lead-free metal halides have attracted extensive attention due to their unique optical properties， low toxicity and excellent environmental stability. In this paper， Cs₂ZnCl₄∶Ce³⁺， Cs₂ZnCl₄∶Mn²⁺ and Cs₂ZnCl₄∶Ce³⁺，Mn²⁺ microcrystals are prepared by hydrothermal method. The phase and luminescence characteristics of the microcrystals are characterized by X-ray diffractometer and fluorescence spectrometer. In a series of Ce³⁺ ions doped and Ce³⁺ and Mn²⁺ ions co-doped Cs₂ZnCl₄ microcrystals， Ce³⁺ ions emit at 254 nm in the ultraviolet region， and its emission peak is at 350 nm， corresponding to the 4f-5d transition of Ce³⁺ ions. In Cs₂ZnCl₄ microcrystals doped with Mn²⁺ ions and Ce³⁺ and Mn²⁺ ions， Mn²⁺ ions all exhibit green light emission in the visible region at 361 nm， and the emission peak is located at 530 nm， which corresponds to the ⁴T₁→⁶A₁ transition of Mn²⁺ ions in tetrahedral environment. In Cs₂ZnCl₄ microcrystals doped with Ce³⁺ and Mn²⁺ ions， the emission spectra of Ce³⁺ and Mn²⁺ ions only have their respective luminescence peaks corresponding to their respective excitation peaks， which is a phenomenon of excitation wavelength dependence. In addition， the compound can be applied to fluorescence anti-counterfeiting and information encryption applications in the future because of its obvious excitation wavelength dependence.

Key words: Lead-free perovskite, Ions doping, Excitation wavelength dependence

CLC Number:

O611.4

Tian-Cheng ZHENG, Yue LI, Yu-Ling LIU, Yong-Bo MA, Xi-Yan LI. Synthesis and Multi-Mode Luminescence Properties of Cs₂ZnCl₄∶Ce³⁺，Mn²⁺[J]. Chinese Journal of Applied Chemistry, 2023, 40(12): 1613-1622.

Figures/Tables 12

Fig.1 Synthesis of （A， B） Cs2ZnCl4∶Ce3+，Mn2+ microcrystals at room temperature；（C） Hydrothermal synthesis of Cs2ZnCl4∶Ce3+，Mn2+ microcrystals

Fig.2 Standard crystal structure of Cs2ZnCl4

Fig.3 （A） Photoluminescence （PL） spectra of Cs2ZnCl4∶10%Ce3+ （a） Fig.1A Room-temperature （R-T） method （Ⅰ），（b） Fig.1B R-T method （Ⅱ），（c） Fig.1C hydrothermal method （Ⅲ）；（B） Photoluminescence excitation （PLE） spectra of Cs2ZnCl4∶10%Ce3+ （a） Fig.1A R-T method （Ⅰ），（b） Fig.1B R-T method （Ⅱ），（c） Fig.1C hydrothermal method （Ⅲ）；（C） PL spectra of Cs2ZnCl4∶10%Ce3+ （a） 120 ℃，（b） 140 ℃，（c） 160 ℃，（d） 180 ℃；（D） PLE spectra of Cs2ZnCl4∶10%Ce3+ （a） 120 ℃，（b） 140 ℃，（c） 160 ℃，（d） 180 ℃

Fig. 4 XRD pattern （a） Cs2ZnCl4 standard card，（b） Cs2ZnCl4∶40%Ce3+，（c） Cs2ZnCl4∶30%Mn2+，（d） Cs2ZnCl4∶40%Ce3+，10%Mn2+

Fig.5 SEM images （A） and elemental mapping images （B-G） of the Cs2ZnCl4∶Ce3+，Mn2+

Fig.6 Morphology and luminescence of Cs2ZnCl4∶40%Ce3+，10%Mn2+

Fig.7 （A） The PL spectra Cs2ZnCl4∶xCe3+（a-f）x=5%， 10%， 20%， 30%， 40%， 50%；（B） The PLE spectrum of Cs2ZnCl4∶xCe3+；（C） The PL intensity of Cs2ZnCl4∶xCe3+ varies with the doping concentration of Ce3+ ions

Fig.8 （A） The PL spectra of Ce3+ ions in Cs2ZnCl4∶40%Ce3+，yMn2+（a-f） y=5%， 10%， 20%， 30%， 40%， 50%；（B） The PL intensity of Ce3+ ions in Cs2ZnCl4∶40%Ce3+，yMn2+ varies with the doping concentration of Mn2+ ions；（C） The PL spectra of Mn2+ ions in Cs2ZnCl4∶40%Ce3+， yMn2+（a-f） y=5%， 10%， 20%， 30%， 40%， 50%；（D） The PL intensity of Mn2+ ions in Cs2ZnCl4∶40%Ce3+，yMn2+ varies with the doping concentration of Mn2+ ions

Fig.9 （A） PL spectrum of Ce3+， Mn2+ ions under 273 nm excitation；（B） Normalized PLE spectra of Ce3+ （a） and Mn2+ （b） ions；（C） Normalized PL spectra of Ce3+ （a） and Mn2+ （b） ions

Fig.10 PL decay curves of （A） Ce3+ and （B） Mn2+ in Cs2ZnCl4∶40%Ce3+，yMn2+ （excited at 300 nm， probed at 350 nm； excited at 361 nm， probed at 530 nm）

Table 1 The calculated average lifetime of Mn2+ ions with different doping concentrations of Mn2+ ions

y（Mn²⁺）

τ/ms

0.05

0.1

0.2

0.3

0.4

0.5

0.99

0.96

0.93

0.91

0.90

Fig.11 Energy state splitting and optical transition of Mn2+ ions with tetrahedral coordination

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Synthesis and Multi-Mode Luminescence Properties of Cs₂ZnCl₄∶Ce³⁺，Mn²⁺

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